CN113185425A - Preparation method of amine bionic curing accelerator - Google Patents
Preparation method of amine bionic curing accelerator Download PDFInfo
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- CN113185425A CN113185425A CN202110466409.2A CN202110466409A CN113185425A CN 113185425 A CN113185425 A CN 113185425A CN 202110466409 A CN202110466409 A CN 202110466409A CN 113185425 A CN113185425 A CN 113185425A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention belongs to the technical field of accelerator preparation, and particularly relates to a preparation method of an amine bionic curing accelerator, according to the characteristic of reactive activity of active groups contained in the existing epoxy and polyurethane adhesive system, 3, 4-dihydroxy ethyl benzoate containing a catechol structure firstly reacts with acetone to perform ketal protection on a catechol group, and then reacts with a compound containing a diamine group to obtain the amine bionic curing accelerator, and based on the fact that an amino group in the accelerator can react with an epoxy group and an isocyanate group, the amine bionic curing accelerator is introduced into the epoxy and polyurethane adhesive system, and the adhesive property of the adhesive in a water environment is effectively improved through the catechol structure; the synthetic method is simple and convenient to use, and the bionic curing accelerator containing amino and catechol structures is generated based on the reaction of the ethyl 3, 4-dihydroxybenzoate compound containing the catechol structure and the diamino compound, and has wide application prospects.
Description
The technical field is as follows:
the invention belongs to the technical field of preparation of accelerators, and particularly relates to a preparation method of an amine bionic curing accelerator, which can be used for obtaining the amine bionic accelerator for improving the mechanical property of an adhesive.
Background art:
mussel is also called as a rainbow, is a bivalve mollusk, has a black brown shell, lives on seashore rocks, is wedge-shaped, has a sharp front end and a wide and round rear end, is generally 6-8 cm long, has a shell length less than 2 times of the shell height, is equal to the two shells, is bilaterally symmetrical, has purple black shell surface, has luster, has fine and obvious growth lines, and grows annularly from the top. The byssus protrudes from the substantially central byssus hole of the foot of the gill, and tough fiber bundles of scleroprotein with shell matrix as the main component, thereby fixing the shell on the rock or seaweed and other animals. The 3, 4-Dihydroxyphenylalanine (DOPA) molecules contained in the mussel byssus protein enable the mussel byssus to have very good underwater adhesion and seawater impact resistance, a catechol structure in the DOPA molecules can form a bidentate hydrogen bond with a substrate and generate a strong coordination bond with metal, metal ions and metal oxides, a benzene ring in the catechol structure can form a cation-pi interaction with the metal ions and form a pi-pi interaction with a polymer with the benzene ring in the molecular structure. Catechol, also known as catechol, of the formula C6H6O2Catechols are mostly present in nature in the form of derivatives: o-methoxyphenol and 2-methoxy-4-methylphenol, which are important components of beech creosote; sympathomimetic amines in mammals: epinephrine and norepinephrine are compounds with a beta-hydroxyethylamine side chain on the benzene ring of catechol (structural formula shown in the specification). The catechol is colorless crystal, has melting point of 105 deg.C, boiling point of 245 deg.C (750 mm Hg), and density of 1.1493 g/cm3(21 deg.C), soluble in water, alcohol, ether, chloroform, pyridine, and alkaline water solution, insoluble in cold benzene, and sublimable by steam distillation. Catechol is a strong reducing agent, is easy to be oxidized into o-benzoquinone, can reduce a furin solution and a silver oxide solution at room temperature, reacts with thionyl chloride to generate catechol sulfite, reacts with o-phenylenediamine to generate phenazine, and reacts with barium hydroxide to generate barium salt, is used for manufacturing rubber hardening agents, electroplating additives, skin antiseptic bactericides, hair dyes, photographic developers and the like, is an important chemical intermediate, and is also an intermediate of bactericides diethofencarb, insecticide propoxur and carbofuran. The introduction of the catechol structure into the existing adhesive system is of great significance in improving the mechanical properties of the adhesive system, and no relevant reports and documents exist in the prior art.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs a preparation method of an amine bionic curing accelerator so as to effectively improve the bonding property of an adhesive in a water environment.
In order to realize the purpose, the preparation method of the amine bionic curing accelerator comprises the following steps: firstly, performing ketal reaction on ethyl 3, 4-dihydroxybenzoate and acetone according to a molar ratio of 0.2-1 to protect phenolic hydroxyl groups, then, reacting with a diamino compound, and deprotecting a catechol structure of an obtained product in an acidic environment to obtain a bionic curing accelerator, wherein the reaction formula is shown in figure 1, wherein R ═ CnH2nN is 2,3,4 …, or a benzene ring and derivatives thereof.
The specific process of the preparation method of the amine bionic curing accelerator comprises two steps of ketal reaction and synthesis of the bionic curing accelerator:
(1) ketal reaction: placing 3, 4-dihydroxy ethyl benzoate and anhydrous acetone into an eggplant-shaped bottle, dropwise adding 2-10ml of phosphorus trichloride acetone solution with the mass percentage concentration of 0.5-5% into the eggplant-shaped bottle, stirring under the protection of nitrogen, reacting at normal temperature overnight to obtain a crude product, dissolving the crude product by using 500ml of diethyl ether of 100-;
(2) synthesizing a bionic curing accelerator: placing the light yellow liquid obtained in the step (1) and a DMF (N, N-dimethylformamide) aqueous solution with the mass percentage concentration of 30-60% into an eggplant-shaped bottle, slowly dropwise adding a diamino compound DMF solution with the mass percentage concentration of 50-90% into the eggplant-shaped bottle, wherein the molar ratio of the light yellow liquid to the diamino compound is 0.5-1.5, stirring under the protection of nitrogen, reacting at normal temperature overnight, dissolving the obtained brown oily substance into the DMF aqueous solution with the mass percentage concentration of 30-60%, adding concentrated hydrochloric acid with the volume ratio fraction of 1-10%, reacting at normal temperature overnight, extracting with ethyl acetate, collecting an organic phase, spin-drying, and passing through a silica gel column to obtain the bionic curing accelerator.
The invention relates to a product after the ketal protection of catechol structure: the mol ratio of the 3, 4-dihydroxy ethyl benzoate to the diamino compound is 0.5-1.5; the diamino compounds include ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, and phenylenediamine.
The bionic curing accelerator prepared by the invention can be applied to the preparation of adhesives of epoxy, polyurethane and polysulfide rubber components by reacting amino groups with epoxy groups and isocyanate groups, and the mechanical property of the adhesives is improved by introducing a catechol structure.
Compared with the prior art, according to the characteristic of reactivity of active groups contained in the existing epoxy and polyurethane adhesive system, ethyl 3, 4-dihydroxybenzoate containing a catechol structure firstly reacts with acetone to perform ketal protection on catechol groups, and then reacts with a compound containing diamine groups to obtain an amine bionic curing accelerator, and based on the fact that amino groups in the accelerator can react with epoxy groups and isocyanate groups, the amine bionic curing accelerator is introduced into the epoxy and polyurethane adhesive system, and the adhesive property of the adhesive in a water environment is effectively improved through the catechol structure; the synthetic method is simple and convenient to use, and the bionic curing accelerator containing amino and catechol structures is generated based on the reaction of the ethyl 3, 4-dihydroxybenzoate compound containing the catechol structure and the diamino compound, and has wide application prospects.
Description of the drawings:
FIG. 1 is a reaction formula of a preparation method of an amine bionic curing accelerator.
FIG. 2 is a hydrogen nuclear magnetic spectrum of a biomimetic curing accelerator synthesized from ethyl 3, 4-dihydroxybenzoate and ethylenediamine according to example 1 of the present invention.
FIG. 3 is a hydrogen nuclear magnetic spectrum of a biomimetic curing accelerator synthesized from ethyl 3, 4-dihydroxybenzoate and propylenediamine according to example 2 of the present invention.
FIG. 4 is a hydrogen nuclear magnetic spectrum of a biomimetic curing accelerator synthesized by ethyl 3, 4-dihydroxybenzoate and hexamethylenediamine according to example 3 of the present invention.
The specific implementation method comprises the following steps:
the invention is further described with reference to the accompanying drawings and the specific implementation method.
Example 1:
the specific process of the preparation method of the amine bionic curing accelerator comprises two steps of ketal reaction and synthesis of the bionic curing accelerator:
(1) placing 3.64g of 3, 4-dihydroxy ethyl benzoate into a 100mL eggplant-shaped bottle, adding 20mL of anhydrous acetone for dissolving, dropwise adding 5mL of phosphorus trichloride acetone solution with mass percent concentration of 2% into the eggplant-shaped bottle as a catalyst, stirring under the protection of nitrogen, reacting at normal temperature overnight to obtain a crude product, dissolving the crude product with 250mL of diethyl ether, washing with 500mL of saturated sodium chloride aqueous solution, collecting an organic phase, spin-drying, passing through a silica gel column to obtain a light yellow liquid, namely a ketal-protected catechol structure product;
(2) placing 2.28g of the light yellow liquid obtained in the step (1) in a 100mL eggplant-shaped bottle, adding 20mL of anhydrous DMF for dissolution, dissolving 0.6g of ethylenediamine in 10mL of anhydrous DMF, slowly dropwise adding the solution into the eggplant-shaped bottle, stirring under the protection of nitrogen, reacting at normal temperature overnight, dissolving the obtained brown oily substance in 200mL of DMF, adding 5mL of concentrated hydrochloric acid, reacting at normal temperature overnight, extracting with ethyl acetate, collecting an organic phase, spin-drying, and passing through a silica gel column to obtain the biomimetic curing accelerator synthesized by ethyl 3, 4-dihydroxybenzoate and ethylenediamine, wherein a hydrogen nuclear magnetic spectrum of the biomimetic curing accelerator is shown in FIG. 2.
Example 2:
the specific process of the preparation method of the amine bionic curing accelerator comprises two steps of ketal reaction and synthesis of the bionic curing accelerator:
(1) same as in step (1) of example 1;
(2) placing 2.28g of the light yellow liquid obtained in the step (1) in a 100mL eggplant-shaped bottle, adding 20mL of anhydrous DMF for dissolution, dissolving 0.89g of propylene diamine in 10mL of anhydrous DMF, slowly dropwise adding the mixture into the eggplant-shaped bottle, stirring the mixture under the protection of nitrogen, reacting the mixture at normal temperature overnight, dissolving the obtained brown oily substance in 300mL of DMF, adding 6mL of concentrated hydrochloric acid, reacting the mixture at normal temperature overnight, extracting the mixture with ethyl acetate, collecting an organic phase, spin-drying the organic phase, and passing the organic phase through a silica gel column to obtain the biomimetic curing accelerator synthesized by ethyl 3, 4-dihydroxybenzoate and propylene diamine, wherein a hydrogen nuclear magnetic spectrum of the biomimetic curing accelerator is shown in FIG. 3.
Example 3:
the specific process of the preparation method of the amine bionic curing accelerator comprises two steps of ketal reaction and synthesis of the bionic curing accelerator:
(1) same as in step (1) of example 1;
(2) placing 2.28g of the light yellow liquid obtained in the step (1) in a 100mL eggplant-shaped bottle, adding 20mL of anhydrous DMF for dissolution, dissolving 0.93g of hexamethylenediamine in 10mL of anhydrous DMF, slowly dropwise adding the solution into the eggplant-shaped bottle, stirring under the protection of nitrogen, reacting at normal temperature overnight, dissolving the obtained brown oily substance in 150mL of DMF, adding 4mL of concentrated hydrochloric acid, reacting at normal temperature overnight, extracting with ethyl acetate, collecting an organic phase, spin-drying, passing through a silica gel column to obtain the biomimetic curing accelerator synthesized by ethyl 3, 4-dihydroxybenzoate and hexamethylenediamine, wherein a hydrogen nuclear magnetic spectrum of the biomimetic curing accelerator is shown in FIG. 4.
Claims (10)
1. A preparation method of an amine bionic curing accelerator is characterized by comprising the following steps: firstly, ethyl 3, 4-dihydroxybenzoate and acetone are subjected to ketal reaction according to the molar ratio of 0.2-1 to protect phenolic hydroxyl groups, and thenThen reacting with a diamino compound, and deprotecting the catechol structure of the obtained product in an acidic environment to obtain the bionic curing accelerator, wherein R ═ C in the reaction formulanH2nN is 2,3,4 …, or a benzene ring and derivatives thereof.
2. The method for preparing the amine bionic curing accelerator according to claim 1, wherein the specific process comprises two steps of ketal reaction and synthesis of the bionic curing accelerator:
(1) ketal reaction: putting 3, 4-dihydroxy ethyl benzoate and anhydrous acetone into an eggplant-shaped bottle, dropwise adding a phosphorus trichloride acetone solution into the eggplant-shaped bottle, stirring under the protection of nitrogen, reacting overnight at normal temperature to obtain a crude product, dissolving the crude product with diethyl ether, washing with a saturated sodium chloride aqueous solution, collecting an organic phase, drying by spinning, and passing through a silica gel column to obtain a light yellow liquid, namely a product protected by the ketal of the catechol structure;
(2) synthesizing a bionic curing accelerator: and (2) placing the light yellow liquid obtained in the step (1) and a DMF (dimethyl formamide) aqueous solution into an eggplant-shaped bottle, slowly dropwise adding the DMF solution of a diamino compound into the eggplant-shaped bottle, stirring under the protection of nitrogen, reacting overnight at normal temperature, dissolving the obtained brown oily substance into the DMF aqueous solution, adding concentrated hydrochloric acid, reacting overnight at normal temperature, extracting with ethyl acetate, collecting an organic phase, drying by spinning, and passing through a silica gel column to obtain the bionic curing accelerator.
3. The method for preparing the amine bionic curing accelerator as claimed in claim 2, wherein the volume of the phosphorus trichloride acetone solution is 2-10ml, and the mass percentage concentration is 0.5-5%.
4. The method for preparing amine bionic curing accelerator as claimed in claim 2 or 3, wherein the volume of the ether is 500ml and the volume of the saturated sodium chloride aqueous solution is 500ml and 1000 ml.
5. The method for preparing the amine bionic curing accelerator as claimed in claim 2, wherein the mass percentage concentration of the DMF aqueous solution is 30-60%.
6. The method for preparing the amine bionic curing accelerator as claimed in claim 2, wherein the mass percentage concentration of the solution of the bisamino compound DMF is 50-90%.
7. The method for preparing the amine bionic curing accelerator as claimed in claim 2, wherein the volume ratio fraction of the concentrated hydrochloric acid is 1-10%.
8. The method for producing an amine-based biomimetic curing accelerator according to claim 1 or 2, characterized in that the ketal-protected product of catechol structure: the mol ratio of the ethyl 3, 4-dihydroxy benzoate to the diamino compound is 0.5-1.5.
9. The method for preparing the amine-based biomimetic curing accelerator according to claim 1 or 2, wherein the diamine compound comprises ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, and phenylenediamine.
10. The preparation method of the amine bionic curing accelerator as claimed in claim 1 or 2, wherein the bionic curing accelerator is applied to the preparation of adhesives of epoxy, polyurethane and polysulfide rubber components by the reaction of amino groups with epoxy groups and isocyanate groups.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521751A (en) * | 2022-11-04 | 2022-12-27 | 南宝树脂（佛山）有限公司 | Seawater-resistant environment-friendly rubber for kayaks and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017528A (en) * | 2015-07-10 | 2015-11-04 | 中山大学 | Preparation method and application of catechol-containing polymer |
| WO2016115360A1 (en) * | 2015-01-14 | 2016-07-21 | Coferon, Inc. | C-myc ligands capable of dimerizing in an aqueous solution, and methods of using same |
| JP2016141769A (en) * | 2015-02-04 | 2016-08-08 | 帝人株式会社 | Hyaluronic acid derivative and medical preparation |
| CN109010827A (en) * | 2018-08-22 | 2018-12-18 | 上海交通大学 | Chlorambucil-poly-dopamine prodrug nanoparticle antitumor application thereof |
-
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- 2021-04-28 CN CN202110466409.2A patent/CN113185425B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016115360A1 (en) * | 2015-01-14 | 2016-07-21 | Coferon, Inc. | C-myc ligands capable of dimerizing in an aqueous solution, and methods of using same |
| JP2016141769A (en) * | 2015-02-04 | 2016-08-08 | 帝人株式会社 | Hyaluronic acid derivative and medical preparation |
| CN105017528A (en) * | 2015-07-10 | 2015-11-04 | 中山大学 | Preparation method and application of catechol-containing polymer |
| CN109010827A (en) * | 2018-08-22 | 2018-12-18 | 上海交通大学 | Chlorambucil-poly-dopamine prodrug nanoparticle antitumor application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张志贤等: "《有机官能团定量分析》", 31 July 1990, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521751A (en) * | 2022-11-04 | 2022-12-27 | 南宝树脂（佛山）有限公司 | Seawater-resistant environment-friendly rubber for kayaks and preparation method thereof |
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